A computational study of samarium diiodide-induced cyclizations of N-oxoalkyl-substituted methyl indole-3-carboxylates-A rationale of the diastereoselectivity.

Title A computational study of samarium diiodide-induced cyclizations of N-oxoalkyl-substituted methyl indole-3-carboxylates-A rationale of the diastereoselectivity.
Authors A.J. Achazi; D. Andrae; H.U. Reissig; B. Paulus
Journal J Comput Chem
DOI 10.1002/jcc.25055
Abstract

A detailed model for the reaction mechanism of the samarium diiodide (SmI2 ) mediated reductive coupling of N-oxoalkyl-substituted methyl indole-3-carboxylates is developed in this study by determining the Gibbs energies for the intermediates of possible reaction pathways. The Gibbs energies at ambient temperature are calculated with dispersion corrected density functional theory in combination with implicit (D-COSMO-RS) and explicit solvent description. Temperature dependent ro-vibrational contributions are considered with the help of statistical thermodynamics. In contrast to previous proposals for the reaction mechanism, the high diastereoselectivity in the cyclization is found to be due to the formation of an energetically highly favorable chelate complex in which the final relative configuration is already preformed. After cyclization and a second electron transfer, alkylation of the resulting anion takes place under kinetic control from the more "open" face whereas protonation is under thermodynamic control. The calculations are in good agreement with these experimental findings. © 2017 Wiley Periodicals, Inc.

Citation A.J. Achazi; D. Andrae; H.U. Reissig; B. Paulus.A computational study of samarium diiodide-induced cyclizations of N-oxoalkyl-substituted methyl indole-3-carboxylates-A rationale of the diastereoselectivity.. J Comput Chem. 2017;38(31):26932700. doi:10.1002/jcc.25055

Related Elements

Samarium

See more Samarium products. Samarium (atomic symbol: Sm, atomic number: 62) is a Block F, Group 3, Period 6 element with an atomic radius of 150.36. Samarium Bohr ModelThe number of electrons in each of samarium's shells is 2, 8, 18, 24, 8, 2 and its electron configuration is [Xe]4f6 6s2. The samarium atom has a radius of 180 pm and a Van der Waals radius of 229 pm. In its elemental form, samarium has a silvery-white appearance. Elemental Samarium PictureSamarium is not found as free element in nature. It is found in the minerals cerite, gadolinite, samarskite, monazite and bastnäsite. Samarium is classified as a rare earth element and is the 40th most abundant element in the Earth's crust. Samarium was discovered and first isolated by Lecoq de Boisbaudran in 1879. It is named after the mineral samarskite, the mineral from which it was isolated.

Iodine

See more Iodine products. Iodine (atomic symbol: I, atomic number: 53) is a Block P, Group 17, Period 5 element with an atomic radius of 126.90447. The number of electrons in each of Iodine's shells is 2, 8, 18, 18, 7 and its electron configuration is [Kr] 4d10 5s2 5p5. The iodine atom has a radius of 140 pm and a Van der Waals radius of 198 pm. In its elemental form, iodine has a lustrous metallic gray appearance as a solid and a violet appearance as a gas or liquid solution. Elemental IodineIodine forms compounds with many elements, but is less active than the other halogens. It dissolves readily in chloroform, carbon tetrachloride, or carbon disulfide. Iodine compounds are important in organic chemistry and very useful in the field of medicine. Iodine was discovered and first isolated by Bernard Courtois in 1811. The name Iodine is derived from the Greek word "iodes" meaning violet.

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